Reactor continuity

ABSTRACT

A dual catalyst system comprising a phosphinimine ligand containing catalyst and phenoxide ligand (preferably a salicylaldimine) on a support treated with a metal salt has improved reactor continuity in a dispersed phase reaction in terms of initial activation and subsequent deactivation The resulting catalyst has a lower consumption of ethylene during initiation and a lower rate of deactivation. Preferably the catalyst is used with an antistatic agent.

FIELD OF THE INVENTION

The present invention relates to improving the continuity of a dual phosphinimine/phenoxide (preferably a salicylaldimine) ligand containing catalyst in a dispersed phase (i.e. gas phase, fluidized bed or stirred bed or slurry phase) olefin polymerization. There are a number of factors which impact on reactor continuity in a dispersed phase polymerization. Particularly there may be fouling which will decrease catalyst productivity and reactor operability. The decrease in catalyst productivity or activity is reflected by a decrease in ethylene uptake over time.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 6,309,997 issued Oct. 30, 2001 to Fujita et al. assigned to Mitsui Chemicals, Inc., teaches an olefin polymerization catalyst using a phenoxide (preferably a salicylaldimine) ligand for use in the polymerization of olefins. These catalysts may be considered single site type catalysts. These catalysts are more active than the prior Ziegler Natta catalysts, which may lead to issues of polymer agglomeration. Additionally, static may contribute to the problem. As a result reactor continuity (e.g. fouling and also catalyst life time) may be a problem.

U.S. Pat. No. 7,064,096 issued Jun. 20, 2006 to Hoang et al, assigned to NOVA Chemicals (International) S.A. discloses a dual phoshpinimine and phenoxide catalyst on a single support. The patent does not disclose or suggest supports treated in accordance with the present invention.

The kinetic profile of many single site catalysts starts off with a very high activity over a relatively short period of time, typically about the first five minutes of the reaction, the profile then goes through an inflection point and decreases rapidly for about the next five minutes and thereafter there is period of relative slower decline in the kinetic profile. This may be measured by the ethylene uptake, typically in standard liters of ethylene per minute in the reactor.

There is no prior art that the Applicant is aware of which expressly discloses a process to modify (improve) the kinetic profile of a catalyst containing a phenoxide (preferably a salicylaldimine) ligand. There are a number of patents which teach modified porous inorganic supports for polymerizations using single site catalysts. However, none of these patents expressly disclose that the kinetic profile of the resulting catalyst is modified.

Above noted U.S. Pat. No. 6,309,997 teaches at columns 114-115 that inorganic oxide supports suitable for use with catalysts containing a phenoxide (preferably a salicylaldimine) ligand may contain a small amount of carbonate, sulfate, nitrate or oxide component, such as Na₂CO₃, K₂CO₃, CaCO₃, MgCO₃, Na₂SO₄, Al₂ (SO₄)₃, BaSO₄, KNO₃, Mg(NO₃)₂, Al(NO₃)₃, Na₂O, K₂O or Li₂O. The patent teaches these may be present as impurities and does not teach adding salts to the substrate.

U.S. Pat. No. 6,734,266 issued May 11, 2004 to Gao et al., assigned to NOVA Chemicals (International) S.A. teaches sulfating the surface of porous inorganic support with an acid, amide or simple salt such as an alkali or alkaline earth metal sulphate. The resulting treated support may be calcined. Aluminoxane and a single site catalyst are subsequently deposited on the support. The resulting catalyst shows improved activity. However, the patent fails to teach or suggest a catalyst containing a phenoxide (preferably a salicylaldimine) ligand.

U.S. Pat. No. 7,001,962 issued Feb. 21, 2006 to Gao et al., assigned to NOVA Chemicals (International) S.A. teaches treating a porous inorganic support with a zirconium compound including zirconium sulphate and an acid such as a fluorophosphoric acid, sulphonic acid, phosphoric acid and sulphuric acid. The support is dried and may be heated under air at 200° C. and under nitrogen up to 600° C. Subsequently a trialkyl aluminum compound (e.g. triethyl aluminum) or an alkoxy aluminum alkyl compound (e.g. diethyl aluminum ethoxide) and a single site catalyst are deposited on the support. The specification teaches away from using aluminoxane compounds. The activity of these supports is typically lower than the activity of the catalyst of U.S. Pat. No. 6,734,266 (compare Table 5 of U.S. Pat. No. 7,001,962 with Table 2 of U.S. Pat. No. 6,734,266). The present invention eliminates the required acid reagent that reacts with the zirconium compound.

Canadian Patent Application 2,716,772 filed Oct. 6, 2010 discloses a process to improve the dispersed phase reactor continuity of catalyst having a phosphinimine ligand by supporting the catalyst on a support treated with a number of compounds including Zr(SO₄)₂.4H₂O. The support is also treated with MAO. This patent application fails to teach a catalyst containing a phenoxide (preferably a salicylaldimine) ligand.

U.S. Pat. No. 7,273,912 issued Sep. 25, 2007 to Jacobsen et al., assigned to Innovene Europe Limited, teaches a catalyst which is supported on a porous inorganic support which has been treated with a sulphate such as ammonium sulphate or an iron, copper, zinc, nickel or cobalt sulphate. The support may be calcined in an inert atmosphere at 200 to 850° C. The support is then activated with an ionic activator and then contacted with a single site catalyst. The patent fails to teach aluminoxane compounds and zirconium sulphate or a catalyst containing a phenoxide (preferably a salicylaldimine) ligand.

U.S. Pat. No. 7,005,400 issued Feb. 28, 2006 to Takahashi assigned to Polychem Corporation teaches a combined activator support comprising a metal oxide support and a surface coating of a group 2, 3, 4, 13 and 14 oxide or hydroxide different from the carrier. The support is intended to activate the carrier without the conventional “activators”. However, in the examples the supported catalyst is used in combination with triethyl aluminum. The triethyl aluminum does not appear to be deposited on the support. The patent teaches away from adding MAO to a support treated with zirconium sulphate tetrahydrate.

U.S. Pat. No. 7,442,750 issued Oct. 28, 2008 to Jacobsen et al., assigned to Innovene Europe Limited teaches treating an inorganic metal oxide support typically with a transition metal salt, preferably a sulphate, of iron, copper, cobalt, nickel, and zinc. Then a single site catalyst containing a cyclopentadienyl ligand, preferably a constrained geometry single site catalyst and an activator are deposited on the support. The activator is preferably a borate but may be an aluminoxane compound. The disclosure appears to be directed at reducing static in the reactor bed and product in the absence of a conventional antistatic agent such as STADIS®. The patent fails to teach or suggest a catalyst containing a phenoxide (preferably a salicylaldimine) ligand.

U.S. Pat. No. 6,653,416 issued Nov. 25, 2003 to McDaniel at al., assigned to Phillips Petroleum Company, discloses a fluoride silica-zirconia or titania porous support for a metallocene catalyst activated with an aluminum compound selected from the group consisting of alkyl aluminums, alkyl aluminum halides and alkyl aluminum alkoxides. Comparative examples 10 and 11 show the penetration of zirconium into silica to form a silica-zirconia support. However, the examples (Table 1) show the resulting catalyst has a lower activity than those when the supports were treated with fluoride.

The use of a salt of a carboxylic acid, especially aluminum stearate, as an antifouling additive to olefin polymerization catalyst compositions is disclosed in U.S. Pat. No. 6,271,325 (McConville et al., to Univation) and U.S. Pat. No. 6,281,306 (Oskam et al., to Univation).

The preparation of supported catalysts using an amine antistatic agent, such as the fatty amine sold under the trademark KEMAMINE®AS-990, is disclosed in U.S. Pat. No. 6,140,432 (Agapiou et al., to Exxon) and U.S. Pat. No. 6,117,955 (Agapiou et al., to Exxon).

Antistatic agents are commonly added to aviation fuels to prevent the build-up of static charges when the fuels are pumped at high flow rates. The use of these antistatic agents in olefin polymerizations is also known. For example, an aviation fuel antistatic agent sold under the trademark STADIS composition (which contains a “polysulfone” copolymer, a polymeric polyamine and an oil soluble sulfonic acid) was originally disclosed for use as an antistatic agent in olefin polymerizations in U.S. Pat. No. 4,182,810 (Wilcox, to Phillips Petroleum). The examples of the Wilcox '810 patent illustrate the addition of the “polysulfone” antistatic agent to the isobutane diluent in a commercial slurry polymerization process. This is somewhat different from the teachings of the earlier referenced patents—in the sense that the carboxylic acid salts or amine antistatics of the other patents were added to the catalyst, instead of being added to a process stream.

The use of “polysulfone” antistatic composition in olefin polymerizations is also subsequently disclosed in:

1) chromium catalyzed gas phase olefin polymerizations, in U.S. Pat. No. 6,639,028 (Heslop et al., assigned to BP Chemicals Ltd.);

2) Ziegler Natta catalyzed gas phase olefin polymerizations, in U.S. Pat. No. 6,646,074 (Herzog et al., assigned to BP Chemicals Ltd.); and

3) metallocene catalyzed olefin polymerizations, in U.S. Pat. No. 6,562,924 (Benazouzz et al., assigned to BP Chemicals Ltd.).

The Benazouzz et al. patent does teach the addition of STADIS antistatic agent to the polymerization catalyst in small amounts (about 150 ppm by weight). However, in each of the Heslop et al. '028, Herzog et al. '074 and Benazouzz et al. '924 patents listed above, it is expressly taught that it is preferred to add the STADIS antistatic directly to the polymerization zone (i.e. as opposed to being an admixture with the catalyst).

The present invention seeks to provide a novel supported dual catalyst system comprising from 20:80 mole % of a phenoxide (preferably a salicylaldimine) ligand containing catalyst and from 80 to 20 mole % of a phosphinimine catalyst, which catalyst systems are suitable for use in a dispersed phase polymerization. Optionally one or more antistatic agents may be added to the support or may be added separately to the dispersed phase polymerization.

SUMMARY OF THE INVENTION

The present invention provides a dual catalyst system comprising:

i) from 20 to 80 mole % of an organo group 3 to 11 metal complex containing one or more phenoxide ligands; and

ii) from 80 to 20 mole % of a phosphinimine catalyst of the formula:

wherein M is a group 4 metal having an atomic weight less than 179; Pl is a phosphinimine ligand; L is a monoanionic ligand selected from the group consisting of a cyclopentadienyl radical which is unsubstituted or substituted by a substituent selected from the group consisting of a C₁₋₆ alkyl radical which is substituted by 2n+1 fluorine atoms where n is the number of carbon atoms in the alkyl radical, and a C₆F₅ radical which cyclopentadienyl ligand is optionally further substituted with up to two C₃₋₆ alkyl radicals [in the 2 or 3 position relative to the fluorine containing substituent]; Y is an activatable ligand; t is 1 or 2; q is 1; and p is an integer and the sum of t+q+p equals the valence state of M; both on a calcined inorganic support impregnated with not less than 1 weight % of Zr(SO₄)₂ to provide from 0.010 to 0.50, mmol of Zr from the sulphate per gram of impregnated support.

In a further embodiment the phenoxide ligand has the formula:

wherein R¹, R², R³, R⁴, R⁵, and R⁶ are independently selected from the group consisting of a hydrogen atom, a heteroatom containing group having up to 20, carbon atoms, and a hydrocarbyl radical containing up to 25 carbon atoms.

In a further embodiment none of R³, R⁴, R⁵ has a Hammett σ_(p) value (Hansch et al., Chem. Rev. 1991, 91, 165) greater than 0.2.

In a further embodiment the catalyst having a phenoxide ligand has the formula:

wherein R¹, R², R³, R⁴, R⁵, and R⁶ are independently selected from the group consisting of a hydrogen atom, a heteroatom containing group having up to 20, carbon atoms, and a hydrocarbyl radical containing up to 25 carbon atoms, M is a Group 3 to 11 transition metal, X is an activatable or leaving group, n is 1 or 2 and m is 2 or 3 and the sum of n+m is the valence of M.

In a further embodiment the phosphinimine ligand has the formula ((R¹⁵)₃P═N)— wherein each R¹⁵ is independently selected from the group consisting of C₁₋₈ alkyl radicals.

In a further embodiment the support further comprises an activator of the formula: R¹² ₂AlO(R¹²AlO)_(q)AlR¹² ₂ wherein each R¹² is independently selected from the group consisting of C₁₋₂₀ hydrocarbyl radicals and r is from 3 to 50 to provide from 50 to 500 parts by weight per part by weight of total M in the dual catalyst.

In a further embodiment X is selected from the group consisting of consisting of a chlorine atom, a methyl radical, an ethyl radical and a benzyl radical.

In a further embodiment Y is selected from the group consisting of a hydrogen atom, a chlorine atom and a C₁₋₄ alkyl radical.

In a further embodiment in the activator R¹² is a C₁₋₄ alkyl radical and r is from 10 to 40.

In a further embodiment the dual catalyst system further comprising from 50 to 250 ppm based on the weight of the supported catalyst of an antistatic comprising:

(i) from 3 to 48 parts by weight of one or more polysulfones comprising:

-   -   (a) 50 mole % of sulphur dioxide;     -   (b) 40 to 50 mole % of a C₆₋₂₀ an alpha olefin; and     -   (c) from 0 to 10 mole % of a compound of the formula ACH═CHB         where A is selected from the group consisting of a carboxyl         radical and a C₁₋₁₅ carboxy alkyl radical and B is a hydrogen         atom or a carboxyl radical provided if A and B are carboxyl         radicals A and B may form an anhydride;

(ii) from 3 to 48 parts by weight of one or more polymeric polyamides of the formula: R²⁰N[(CH₂CHOHCH₂NR²¹)_(a)—(CH₂CHOHCH₂NR²¹—R²²—NH)_(b)—(CH₂CHOHCH₂NR²³)_(c)H_(x)]H_(2-x) wherein R²¹ is an aliphatic hydrocarbyl group of 8 to 24 carbon atoms; R²² is an alkylene group of 2 to 6 carbon atoms; R²³ is the group R²²—HNR²¹; R²⁰ is R²¹ or an N-aliphatic hydrocarbyl alkylene group having the formula R²¹NHR²²; a, b and c are integers from 0 to 20 and x is 1 or 2; with the proviso that when R²⁰ is R²¹ then a is greater than 2 and b=c=0, and when R²⁰ is R²¹NHR²² then a is 0 and the sum of b+c is an integer from 2 to 20; and

(iii) from 3 to 48 parts by weight of C₁₀₋₂₀ alkyl or arylalkyl sulphonic acid.

In a further embodiment in the phenoxy ligand R¹ is a cyclohexyl radical, R⁴ is a methoxy radical and R⁶ is a t-butyl radical.

In a further embodiment there is provided a process for preparing the above dual catalyst system, comprising:

(i) impregnating a porous particulate inorganic oxide support having an average particle size from 10 to 150 microns, a surface area greater than 100 m²/g and a pore volume greater than 0.3 ml/g with

(ii) an aqueous solution of Zr(SO₄)₂.4H₂O and hydrates thereof to provide not less than 1 weight % based on the weight of the support of said salt;

(iii) calcining said impregnated support at a temperature from 300° C. to 600° C. for a time from 2 to 20 hours in an inert atmosphere;

(iv) contacting said calcined support with a hydrocarbyl solution containing at least 5 weight % of an aluminum activator compound of the formula R¹² ₂AlO(R¹²AlO)_(q)AlR¹² ₂ wherein each R¹² is independently selected from the group consisting of C₁₋₂₀ hydrocarbyl radicals and r is from 3 to 50 to provide from 10 to 60 weight % of said aluminum compound based on the weight of said calcined support; optionally separating said activated support from said hydrocarbyl solution; and contacting said activated support with one or more hydrocarbyl solutions containing a phosphinimine catalyst, a phenoxide ligand containing catalyst or both to provide from 0.1 to 30 weight % of said catalysts (based on the weight of the calcined support); and

(v) recovering and drying the catalyst.

In a further embodiment there is provided a disperse phase polymerization process comprising contacting one or more C₂₋₈ alpha olefins with a dual catalyst system as above, and feeding to the reactor from 10 to 80 ppm based on the weight of the polymer produced of an antistatic comprising:

(i) from 3 to 48 parts by weight of one or more polysulfones comprising:

-   -   (a) 50 mole % of sulphur dioxide;     -   (b) 40 to 50 mole % of a C₆₋₂₀ an alpha olefin; and     -   (c) from 0 to 10 mole % of a compound of the formula ACH═CHB         where A is selected from the group consisting of a carboxyl         radical and a C₁₋₁₅ carboxy alkyl radical and B is a hydrogen         atom or a carboxyl radical provided if A and B are carboxyl         radicals A and B may form an anhydride;

(ii) from 3 to 48 parts by weight of one or more polymeric polyamides of the formula: R²⁰N[(CH₂CHOHCH₂NR²¹)_(a)—(CH₂CHOHCH₂NR²¹—R²²—NH)_(b)—(CH₂CHOHCH₂NR²³)_(c)H_(x)]H_(2-x) wherein R²¹ is an aliphatic hydrocarbyl group of 8 to 24 carbon atoms; nm R²² is an alkylene group of 2 to 6 carbon atoms; R²³ is the group R²²—HNR²¹; R²⁰ is R²¹ or an N-aliphatic hydrocarbyl alkylene group having the formula R²¹NHR²²; a, b and c are integers from 0 to 20 and x is 1 or 2; with the proviso that when R²⁰ is R²¹ then a is greater than 2 and b=c=0, and when R²⁰ is R²¹NHR²² then a is 0 and the sum of b+c is an integer from 2 to 20; and

(iii) from 3 to 48 parts by weight of C₁₀₋₂₀ alkyl or arylalkyl sulphonic acid.

In a further embodiment, there is provided disperse phase polymerization process comprising contacting one or more C₂₋₈ alpha olefins with a dual catalyst system which also comprises an antistatic agent.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is the kinetic profile of the catalysts run in example 1.

DETAILED DESCRIPTION

As used in this specification dispersed phase polymerization means a polymerization in which the polymer is dispersed in a fluid polymerization medium. The fluid may be liquid in which case the polymerization would be a slurry phase polymerization or the fluid could be gaseous in which case the polymerization would be a gas phase polymerization, either fluidized bed or stirred bed.

As used in this specification dual catalyst system refers to a system in which two catalysts are used on the same support (in contrast to a mixed catalyst system in which a polymerization is conducted in the presence of a mixture of different catalyst on separate supports (e.g. a mixture of supported phosphinimine catalyst and supported phenoxide catalysts).

As used in this specification kinetic profile means a plot of ethylene consumption in standard liters of ethylene per minute against time in minutes, corrected for the volume of ethylene in the reactor prior to the commencement of the reaction, in a 2 liter reactor over a period of time from 0 to 60 minutes.

As used in this specification gram of supported catalyst means a gram of the dual catalyst system and activator on the support treated with Zr(SO₄)₂.4H₂O.

The Support

The support for the catalysts of the present invention comprises a silica oxide substrate having a pendant reactive moiety. The reactive moiety may be a siloxyl radical but more typically is a hydroxyl radical. The support should have an average particle size from about 10 to 150 microns, preferably from about 20 to 100 microns. The support should have a large surface area typically greater than about 100 m²/g, preferably greater than about 250 m²/g, most preferably from 300 m²/g to 1,000 m²/g. The support will be porous and will have a pore volume from about 0.3 to 5.0 ml/g, typically from 0.5 to 3.0 ml/g.

Silica suitable for use as a support in the present invention is amorphous. For example, some commercially available silica's are marketed under the trademark of SYLOPOL® 958, 955 and 2408 by Davison Catalysts a Division of W. R. Grace and Company and ES70 and ES70W by PQ Corporation.

The resulting support is in the form of a free flowing dry powder.

Treatment of the Support

The support is treated with an aqueous solution of Zr(SO₄)₂.4H₂O. The support need not be dried or calcined as it is contacted with an aqueous solution.

Generally a 2 to 50, typically a 5 to 15, preferably an 8 to 12, most preferably a 9 to 11 weight % aqueous solution of Zr(SO₄)₂.4H₂O is used to treat the support. The support is contacted with the solution of Zr(SO₄)₂.4H₂O at a temperature from 10° C. to 50° C., preferably from 20 to 30° C., for a time of not less than 30 minutes, typically from 1 to 10 hours, preferably from 1 to 4 hours, until the support is thoroughly impregnated with the solution.

The impregnated support is then recovered typically by drying at an elevated temperature from 100° C. to 150° C., preferably from 120° C. to 140° C., most preferably from 130° C. to 140° C., for about 8 to 12 hours (e.g. overnight). Other recovery methods would be apparent to those skilled in the art.

The dried impregnated support is then calcined. It is important that the support be calcined prior to the initial reaction with an aluminum activator, catalyst or both. Generally, the support may be heated at a temperature of at least 200° C. for up to 24 hours, typically at a temperature from 500° C. to 675° C., preferably from 550° C. to 600° C. for about 2 to 20, preferably 4 to 10 hours. The resulting support will be free of adsorbed water and should have a surface hydroxyl content from about 0.1 to 5 mmol/g of support, preferably from 0.5 to 3 mmol/g of support.

The amount of the hydroxyl groups in silica may be determined according to the method disclosed by J. B. Peri and A. L. Hensley, Jr., in J. Phys. Chem., 72 (8), 2926, 1968, the entire contents of which are incorporated herein by reference.

The Zr(SO₄)₂ is substantially unchanged by calcining under the conditions noted above. At higher temperatures the Zr(SO₄)₂ starts to be converted to ZrO.

The resulting dried and calcined support is then contacted sequentially with the activator and the catalyst in an inert hydrocarbon diluent.

The Activator

The activator is an aluminoxane compound of the formula R¹² ₂AlO(R¹²AlO)_(q)AlR¹² ₂ wherein each R¹² is independently selected from the group consisting of C₁₋₂₀ hydrocarbyl radicals and r is from 3 to 50. In the aluminum activator preferably R¹² is a C₁₋₄ alkyl radical, preferably a methyl radical and r is from 10 to 40. Optionally, a hindered phenol may be used in conjunction with the aluminoxane to provide a molar ratio of Al:hindered phenol from 2:1 to 5:1 if the hindered phenol is present. Generally the molar ratio of Al:hindered phenol, if it is present, is from 3.25:1 to 4.50:1. Preferably the phenol is substituted in the 2, 4 and 6 position by a C₂₋₆ alkyl radical. Desirably the hindered phenol is 2,6-di-tert-butyl-4-ethyl-phenol.

The aluminum compounds (aluminoxanes and optionally hindered phenol) are typically used as activators in substantial molar excess compared to the total amount of metal in the catalysts (e.g. group 3 to 11, preferably 4 to 6 transition metal in the phenoxide catalyst and group 4 transition metal in the phosphinimine catalyst). Aluminum:total metal (in the catalyst) molar ratios may range from 10:1 to 10,000:1, preferably 10:1 to 500:1, most preferably from 50:1 to 150:1, especially from 90:1 to 120:1.

Typically the loading of the alminoxane compound may range from 10 up to 60 weight % preferably from 15 to 50 weight %, most preferably from 20 to 40 weight % based on the weight of the calcined support impregnated with metal salt.

The aluminoxane is added to the support in the form of a hydrocarbyl solution, typically at a 5 to 30 weight % solution, preferably an 8 to 12 weight % solution, most preferably a 9 to 10 weight % solution. Suitable hydrocarbon solvents include C₅₋₁₂ hydrocarbons which may be unsubstituted or substituted by C₁₋₄ alkyl group such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, toluene, or hydrogenated naphtha. An additional solvent is Isopar™ E (C₈₋₁₂ aliphatic solvent, Exxon Chemical Co.).

The treated support may optionally be filtered and/or dried under an inert atmosphere (e.g. N₂) and optionally at reduced pressure, preferably at temperatures from room temperature up to about 80° C.

The optionally dried support with activator is then contacted with the catalyst again in a hydrocarbyl solution.

In an alternate embodiment the support could be treated with a combined solution of activator and catalyst(s). However care needs to be taken with this approach as prolonged contact (e.g. more than about 15 minutes) of the activator with the catalyst may result in degradation of one or both catalysts.

The Catalysts

Phenoxide Containing Catalyst

One catalyst comprises an organo group III to XI transition metal complex containing a phenoxide, preferably a salicylaldimine) ligand. Preferably the metal is a group 4 or 5 transition metal having an atomic number not greater than 73. Most preferably the metal is selected from the group consisting of Ti, Zr, and Hf.

The phenoxide (salicylaldimine) ligand may have the formula:

wherein R¹, R², R³, R⁴, R⁵, and R⁶ are independently selected from the group consisting of a hydrogen atom, a heteroatom containing group having up to 20, preferably from 1 to 18, most preferably from 1 to 12 carbon atoms, and a hydrocarbyl radical containing up to 25 carbon atoms. Preferably, R¹ is selected from the group consisting of a hydrogen atom, alkyl radicals having up to 15, preferably from 1 to 8, most preferably from 1 to 6 carbon atoms, aryl radicals having up to 25, preferably from 6 to 18, most preferably from 6 to 12 carbon atoms, alkoxy radicals having up to 15, preferably from 1 to 8, most preferably from 1 to 6 carbon atoms, and amido radicals which are unsubstituted or substituted by up to two alkyl radicals containing up to 15, preferably from 1 to 8, most preferably from 1 to 6 carbon atoms. In some embodiments R¹ is a C₆₋₁₂ cyclic alkyl radical such as a cyclohexyl radical. In some embodiments R⁶ is a branched C₁₋₆ alkyl radical such as a t-butyl radical. In some embodiments R⁴ is a C₁₋₆ alkoxy radical such as a methoxy radical.

In some embodiments of the invention none of these substituent groups has a Hammett σ_(p) value greater than 0.20.

The phenoxide (salicylaldimine) ligand containing catalyst has the formula:

wherein R¹, R², R³, R⁴, R⁵, and R⁶ are as defined above and M is group III to XI transition metal, preferably a group 4 or 5 transition metal having an atomic number not greater than 73, most preferably selected from the group consisting of Ti, Zr, and Hf, X is an activatable group, and n is 1 or 2 and m is 3 or 2 and the sum of n+m is the valence of M.

Activatable or leaving groups are well known to those skilled in the art. Generally, they may be selected from the group consisting of a halogen atom, alkyl radicals having up to 15, preferably from 1 to 8, most preferably from 1 to 6 carbon atoms, aryl radicals having up to 25, preferably from 6 to 18, most preferably from 6 to 12 carbon atoms, alkoxy radicals having up to 15, preferably from 1 to 8, most preferably from 1 to 6 carbon atoms, amido radicals which are unsubstituted or substituted by up to two alkyl radicals containing up to 15, preferably from 1 to 8, most preferably from 1 to 6 carbon atoms, and phenoxy radicals having up to 18, preferably from 6 to 12 carbon atoms.

The synthesis of desired ligands can be accomplished by reaction of salicylaldehydes with amines. Preparation of the requisite salicylaldehydes can be accomplished using standard synthetic techniques. Some synthetic methods for preparing the phenoxide ligands are disclosed in above noted U.S. Pat. No. 6,309,997 at column 141.

Metallation of the ligands can be accomplished by reaction with basic reagents such as Zr(CH₂Ph)₄. Reaction of the ligands with Zr(CH₂Ph)₄ occurs with elimination of toluene. Alternately, ligands can be deprotonated with reagents such as BuLi, KH or Na metal and then reacted with metal halides, such as ZrCl₄.

Phosphinimine Catalyst

The second component of the catalyst system (second catalyst) is a catalyst of the formula:

wherein M is a group 4 metal having an atomic weight less than 179; Pl is a phosphinimine ligand; L is a monoanionic ligand selected from the group consisting of a cyclopentadienyl radical which is unsubstituted or substituted by a substituent selected from the group consisting of a C₁₋₆ alkyl radical which is substituted by 2n+1 fluorine atoms where n is the number of carbon atoms in the alkyl radical, and a C₆F₅ radical which cyclopendadienyl ligand is optionally further substituted with up to two C₃₋₆ alkyl radicals in the 2 or 3 position relative to the fluorine containing substituent; Y is an activatable ligand; t is 1 or 2; q is 1; and p is an integer and the sum of t+q+p equals the valence state of M.

The preferred metals (M) are from Group 4 (especially titanium, hafnium or zirconium) with titanium being most preferred (e.g. with an atomic weight less than 179).

The phosphinimine ligand is defined by the formula:

wherein each R¹⁵ is independently selected from the group consisting of a C₁₋₈, preferably C₁₋₆ hydrocarbyl radicals which are unsubstituted or further substituted by a halogen atom. Most preferably the phosphinimine ligand is tris t-butyl phosphinimine.

In the phosphinimine catalyst preferably Y is selected from the group consisting of a hydrogen atom; a halogen atom, a C₁₋₁₀ hydrocarbyl radical; a C₁₋₁₀ alkoxy radical; a C₅₋₁₀ aryl oxide radical; each of which said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted by or further substituted by one or more substituents selected from the group consisting of a halogen atom; a C₁₋₈ alkyl radical; a C₁₋₈ alkoxy radical; a C₆₋₁₀ aryl or aryloxy radical; an amido radical which is unsubstituted or substituted by up to two C₁₋₈ alkyl radicals; and a phosphido radical which is unsubstituted or substituted by up to two C₁₋₈ alkyl radicals. Most preferably, Y is selected from the group consisting of a hydrogen atom, a chlorine atom and a C₁₋₄ alkyl radical.

In the above catalyst formulae a number of substituents have a carbon chain length of greater than about 10 carbon atoms. However, one of ordinary skill in the art would predict that lower carbon chain lengths would likely be more effective in view of a number of considerations. Typically one of ordinary skill in the art would consider substituents having less than 10 carbons, preferably less than 8, most preferably less than 6 atoms to be preferred over longer chain length substituents. Similarly with cyclic or aromatic substituents smaller ring sizes of less than about 10 carbon atoms are preferred over larger ring sizes.

The loading of the catalysts on the support should be such to provide from about 0.010 to 0.50, preferably from 0.015 to 0.40, most preferably from 0.015 to 0.035 mmol of metal M, preferably group 4 metal (e.g. Ti) from the catalysts per gram of support (support treated with Zr(SO₄)₂.4H₂O)) and calcined and treated with an activator).

The catalyst containing the phenoxide (preferably salicylaldimine) ligand may be added to the support in a hydrocarbyl solvent such as those noted above. The concentration of phenoxide (preferably salicylaldimine) ligand containing catalyst in the solvent is not critical. Typically, it may be present in the solution in an amount from about 5 to 15 weight %.

The catalyst containing the phosphinimine ligand also may be added to the support in a hydrocarbyl solvent such as those noted above. The concentration of phosphinimine ligand containing catalyst in the solvent is not critical. Typically, it may be present in the solution in an amount from about 5 to 15 weight %.

The catalysts may be added to the activated support either separately as separate solutions or in combination in a single solution.

The supported catalyst (e.g. support, Zr(SO₄)₂, activator and catalyst) typically has a reactivity in a dispersed phase reaction (e.g. gas or slurry phase) greater than 2,500 g of polymer per gram of support, preferably greater than 2,800 g of polyethylene per gram of supported catalyst per hour normalized to an ethylene partial pressure of 200 psig (1379 kPa) and a temperature of 90° C. in the presence of 1-hexene comonomer.

The supported catalyst of the present invention may be used in dispersed phase polymerizations in conjunction with a scavenger such as an aluminum alkyl of the formula Al(R³⁰)₃ wherein R³⁰ is selected from the group consisting of C₁₋₁₀ alkyl radicals, preferably C₂₋₄ alkyl radicals. The scavenger may be used in an amount to provide a molar ratio of Al:Ti from 20 to 2000, preferably from 50 to 1000, most preferably 100 to 500. Generally the scavenger is added to the reactor prior to the catalyst and in the absence of additional poisons, over time declines to 0.

The supported dual catalyst will have a kinetic profile for a plot of ethylene consumption in standard liters of ethylene per minute against time in minutes, corrected for the volume of ethylene in the reactor prior to the commencement of the reaction, in a 2 liter reactor over a period of time from 0 to 60 minutes is such that the ratio of the maximum peak height over the first 10 minutes to the average ethylene consumption from 10 to 60 minutes taken at not less than 40, preferably greater than 60, most preferably from 120 to 300 data points, is less than 3.00, preferably less than 2.50.

The supported dual catalyst may be used in conjunction with an antistatic agent. In one embodiment the antistatic is added directly to the supported dual catalyst. The antistatic may be added in an amount from 0 (e.g. optionally) up to 150,000 parts per million (ppm), preferably from 15,000 up to 120,000 ppm based on the weight of the supported dual catalyst.

In a further embodiment the antistatic may be added to the reactor in an amount from 0 to 100, preferably from 10 to 80 ppm based on the weight of the polymer produced (i.e. the weight of polymer in the fluidized bed or the weight of polymer dispersed in the slurry phase reactor). If present the antistatic agent may be present in an amount from about 0 to 100, preferably from about 10 to 80, most preferably from 20 to 50 ppm based in the weight of polymer. From the productivity of the dual catalyst it is fairly routine to determine the feed rate of the antistatic to the reactor based on the dual catalyst feed rate.

Antistatic “Polysulfone” Additive

The antistatic polysulfone additive comprises at least one of the components selected from:

(1) a polysulfone copolymer;

(2) a polymeric polyamine; and

(3) an oil-soluble sulfonic acid, and, in addition, a solvent for the polysulfone copolymer.

Preferably, the antistatic additive comprises at least two components selected from above components (1), (2) and (3). More preferably, the antistatic additive comprises a mixture of (1), (2) and (3).

According to the present invention, the polysulfone copolymer component of the antistatic additive (often designated as olefin-sulfur dioxide copolymer, olefin polysulfones, or poly(olefin sulfone)) is a polymer, preferably a linear polymer, wherein the structure is considered to be that of alternating copolymers of the olefins and sulfur dioxide, having a one-to-one molar ratio of the comonomers with the olefins in head to tail arrangement. Preferably, the polysulfone copolymer consists essentially of about 50 mole percent of units of sulfur dioxide, about 40 to 50 mole percent of units derived from one or more 1-alkenes each having from about 6 to 24 carbon atoms, and from about 0 to 10 mole percent of units derived from an olefinic compound having the formula ACH═CHB where A is a group having the formula —(C_(x)H_(2x))—COOH wherein x is from 0 to about 17, and B is hydrogen or carboxyl, with the provision that when B is carboxyl, x is 0, and wherein A and B together can be a dicarboxylic anhydride group.

Preferably, the polysulfone copolymer employed in the present invention has a weight average molecular weight in the range 10,000 to 1,500,000, preferably in the range 50,000 to 900,000. The units derived from the one or more 1-alkenes are preferably derived from straight chain alkenes having 6-18 carbon atoms, for example 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene and 1-octadecene. Examples of units derived from the one or more compounds having the formula ACH═CHB are units derived from maleic acid, acrylic acid, 5-hexenoic acid.

A preferred polysulfone copolymer is 1-decene polysulfone having an inherent viscosity (measured as a 0.5 weight percent solution in toluene at 30° C.) ranging from about 0.04 dl/g to 1.6 dl/g.

The polymeric polyamines that can be suitably employed in the antistatic of the present invention are described in U.S. Pat. No. 3,917,466, in particular at column 6 line 42 to column 9 line 29.

The polyamine component in accordance with the present invention has the general formula: R²⁰N[(CH₂CHOHCH₂NR²¹)_(a)—(CH₂CHOHCH₂NR²¹—R²²—NH)_(b)—(CH₂CHOHCH₂NR²³)_(c)H]_(x)H_(2-x—) wherein R²¹ is an aliphatic hydrocarbyl group of 8 to 24 carbon atoms; R²² is an alkylene group of 2 to 6 carbon atoms; R²³ is the group R²²—HNR^(21; R) ²⁰ is R²¹ or an N-aliphatic hydrocarbyl alkylene group having the formula R²¹NHR²²; a, b and c are integers from 0 to 20 and x is 1 or 2; with the proviso that when R²⁰ is R²¹ then a is greater than 2 and b=c=0, and when R²⁰ is R²¹NHR²² then a is 0 and the sum of b+c is an integer from 2 to 20.

The polymeric polyamine may be prepared for example by heating an aliphatic primary monoamine or N-aliphatic hydrocarbyl alkylene diamine with epichlorohydrin in the molar proportion of from 1:1 to 1:1.5 at a temperature of 50° C. to 100° C. in the presence of a solvent, (e.g. a mixture of xylene and isopropanol) adding a strong base, (e.g. sodium hydroxide) and continuing the heating at 50 to 100° C. for about 2 hours. The product containing the polymeric polyamine may then be separated by decanting and then flashing off the solvent.

The polymeric polyamine is preferably the product of reacting an N-aliphatic hydrocarbyl alkylene diamine or an aliphatic primary amine containing at least 8 carbon atoms and preferably at least 12 carbon atoms with epichlorohydrin. Examples of such aliphatic primary amines are those derived from tall oil, tallow, soy bean oil, coconut oil and cotton seed oil. The polymeric polyamine derived from the reaction of tallowamine with epichlorohydrin is preferred. A method of preparing such a polyamine is disclosed in U.S. Pat. No. 3,917,466, column 12, preparation B.1.0

The above-described reactions of epichlorohydrin with amines to form polymeric products are well known and find extensive use in epoxide resin technology.

A preferred polymeric polyamine is a 1:1.5 mole ratio reaction product of N-tallow-1,3-diaminopropane with epichlorohydrin. One such reaction product is “Polyflo™ 130” sold by Universal Oil Company.

According to the present invention, the oil-soluble sulfonic acid component of the antistatic is preferably any oil-soluble sulfonic acid such as an alkanesulfonic acid or an alkylarylsulfonic acid. A useful sulfonic acid is petroleum sulfonic acid resulting from treating oils with sulfuric acid.

Preferred oil-soluble sulfonic acids are dodecylbenzenesulfonic acid and dinonylnaphthylsulfonic acid.

The antistatic additive preferably comprises 1 to 25 weight % of the polysulfone copolymer, 1 to 25 weight % of the polymeric polyamine, 1 to 25 weight % of the oil-soluble sulfonic acid and 25 to 95 weight % of a solvent. Neglecting the solvent, the antistatic additive preferably comprises about 5 to 70 weight % polysulfone copolymer, 5 to 70 weight % polymeric polyamine and 5 to 70 weight % oil-soluble sulfonic acid and the total of these three components is preferably 100%.

Suitable solvents include aromatic, paraffin and cycloparaffin compounds. The solvents are preferably selected from among benzene, toluene, xylene, cyclohexane, fuel oil, isobutane, kerosene and mixtures thereof.

According to a preferred embodiment of the present invention, the total weight of components (1), (2), (3) and the solvent represents essentially 100% of the weight of the antistatic additive.

One useful composition, for example, consists of 13.3 weight % 1:1 copolymer of 1-decene and sulfur dioxide having an inherent viscosity of 0.05 determined as above, 13.3 weight % of “Polyflo™130” (1:1.5 mole ratio reaction product of N-tallow-1,3-diaminopropane with epichlorohydrin), 7.4 weight % of either dodecylbenzylsulfonic acid or dinonylnaphthylsulfonic acid, and 66 weight % of an aromatic solvent which is preferably toluene or kerosene.

Another useful composition, for example, consists of 2 to 7 weight % 1:1 copolymer of 1-decene and sulfur dioxide having an inherent viscosity of 0.05 determined as above, 2 to 7 weight % of “Polyflo™130” (1:1.5 mole ratio reaction product of N-tallow-1,3-diaminopropane with epichlorohydrin), 2 to 8 weight % of either dodecylbenzylsulfonic acid or dinonylnaphthylsulfonic acid, and 78 to 94 weight % of an aromatic solvent which is preferably a mixture of 10 to 20 weight % toluene and 62 to 77 weight % kerosene.

According to a preferred embodiment of the present invention, the antistatic is a material sold by Octel under the trade name STADIS, preferably STADIS 450, more preferably STADIS 425.

Gas Phase Polymerization

Fluidized bed gas phase reactors to make polyethylene are generally operated at low temperatures from about 50° C. up to about 120° C. (provided the sticking temperature of the polymer is not exceeded) preferably from about 75° C. to about 110° C. and at pressures typically not exceeding 3,447 kPa (about 500 psi) preferably not greater than about 2,414 kPa (about 350 psi).

Gas phase polymerization of olefins is well known. Typically, in the gas phase polymerization of olefins (such as ethylene) a gaseous feed stream comprising of at least about 80 weight % ethylene and the balance one or more C₃₋₆ copolymerizable monomers typically, 1-butene, or 1-hexene or both, together with a ballast gas such as nitrogen, optionally a small amount of C₁₋₂ alkanes (i.e. methane and ethane) and further optionally a molecular weight control agent (typically hydrogen) is fed to a reactor and in some cases a condensable hydrocarbon (e.g. a C₄₋₆ alkane such as pentane). Typically, the feed stream passes through a distributor plate at the bottom of the reactor and vertically traverses a bed of polymer particles with active catalyst, typically a fluidized bed but the present invention also contemplates a stirred bed reactor. A small proportion of the olefin monomers in the feed stream react with the catalyst. The unreacted monomer and the other non-polymerizable components in the feed stream exit the bed and typically enter a disengagement zone where the velocity of the feed stream is reduced so that entrained polymer falls back into the fluidized bed. Typically the gaseous stream leaving the top of the reactor is then passed through a compressor. The compressed gas is then cooled by passage through a heat exchanger to remove the heat of reaction. The heat exchanger may be operated at temperatures below about 65° C., preferably at temperatures from 20° C. to 50° C. If there is a condensable gas it is usually condensed and entrained in the recycle stream to remove heat of reaction by vaporization as it recycles through the fluidized bed.

Polymer is removed from the reactor through a series of vessels in which monomer is separated from the off gases. The polymer is recovered and further processed. The off gases are fed to a monomer recovery unit. The monomer recovery unit may be selected from those known in the art including a distillation tower (i.e. a C₂ splitter), a pressure swing adsorption unit and a membrane separation device. Ethylene and hydrogen gas recovered from the monomer recovery unit are fed back to the reactor. Finally, make up feed stream is added to the reactor below the distributor plate.

Slurry Polymerization

Slurry processes are conducted in the presence of a hydrocarbon diluent such as an alkane (including isoalkanes), an aromatic or a cycloalkane. The diluent may also be the alpha olefin comonomer used in copolymerizations. Preferred alkane diluents include propane, butanes, (i.e. normal butane and/or isobutane), pentanes, hexanes, heptanes and octanes. The monomers may be soluble in (or miscible with) the diluent, but the polymer is not (under polymerization conditions). The polymerization temperature is preferably from about 5° C. to about 200° C., most preferably less than about 110° C. typically from about 10° C. to 80° C. The reaction temperature is selected so that the ethylene copolymer is produced in the form of solid particles. The reaction pressure is influenced by the choice of diluent and reaction temperature. For example, pressures may range from 15 to 45 atmospheres (about 220 to 660 psi or about 1500 to about 4600 kPa) when isobutane is used as diluent (see, for example, U.S. Pat. No. 4,325,849) to approximately twice that (i.e. from 30 to 90 atmospheres—about 440 to 1300 psi or about 3000-9100 kPa) when propane is used (see U.S. Pat. No. 5,684,097). The pressure in a slurry process must be kept sufficiently high to keep at least part of the ethylene monomer in the liquid phase.

The reaction typically takes place in a jacketed closed loop reactor having an internal stirrer (e.g. an impeller) and at least one settling leg. Catalyst, monomers and diluents are fed to the reactor as liquids or suspensions. The slurry circulates through the reactor and the jacket is used to control the temperature of the reactor. Through a series of let down valves the slurry enters a settling leg and then is let down in pressure to flash the diluent and unreacted monomers and recover the polymer generally in a cyclone. The diluent and unreacted monomers are recovered and recycled back to the reactor.

The slurry polymerization process can also take place in a continuous stirred tank reactor.

The Polymer

The resulting polymer may have a density from about 0.910 g/cc to about 0.960 g/cc. The resulting polymers may be used in a number of applications such as blown and cast films, extrusion and both injection and rotomolding applications. Typically the polymer may be compounded with the usual additives including heat and light stabilizers such as hindered phenols; ultra violet light stabilizers such as hindered amine stabilizers (HALS); process aids such as fatty acids or their derivatives and fluoropolymers optionally in conjunction with low molecular weight esters of polyethylene glycol.

EXAMPLES Synthesis of ((bis-[N-3tert-butyl-4-methoxy-salicyladimine)cyclohexylamino]zirconium(IV)dichloride) Phenoxide Catalyst

The catalyst was prepared as described in U.S. Pat. No. 7,064,096 issued Jun. 20, 2006 to Hoang et al., assigned to NOVA Chemicals (International) S.A. as described at columns 13 and 14 (Synthesis of Catalyst Component 1). EtMgBr (100 mL, 3M solution in diethyl ether) was added dropwise to a solution of 4-methoxy-2-tert-butyl-phenol (290 mmol) in tetrahydrofuran (THF) (350 mL) at ambient temperature to give an amber solution. After 2 hours of stirring, toluene (250 mL) was added, and the ether and THF were removed by distillation. Triethylamine (60.6 mL) and paraformaldehyde (21.8 g) were then added as a white slurry in toluene. The reaction was stirred overnight, followed by heating for 2 hours at 95° C. to give a cloudy orange solution. The resulting reaction mixture was poured into 1M HCl while cooling to 0° C. The organic layer was separated and the aqueous phase extracted with diethyl ether. The combined organic phases were dried over Na₂SO₄, and then evaporated to give an oily orange material. The oil was dissolved in ethanol (250 mL) and to the clear orange solution was added cyclohexylamine (32.9 mL). The reaction was stirred for 48 hours giving a dark orange solution. The solution was cooled in a freezer causing a yellow crystalline solid to separate. The product was isolated by filtration and washed with cold ethanol. The imine product (54 mmol) was dissolved in THF (200 mL) and added dropwise to a stirring suspension of excess NaH (70 mmol) in THF (250 mL). The yellow suspension was stirred for 48 hours, the excess NaH removed by filtration and the solvent removed to give a bright yellow solid. The sodium salt (46 mmol) was dissolved in THF (150 mL) and added to a suspension of ZrCl₄.THF₂ (23 mmol) in THF (150 mL). The resulting yellow suspension was stirred for 48 hours. The solvent was removed giving impure product as a very sparingly soluble yellow residue. The crude material was extracted with several portions of CH₂Cl₂ followed by filtration and solvent removal to give a yellow solid which was further washed with cold CH₂Cl₂/ether to remove unreacted ligand.

Phosphinimine Catalyst

-   Phosphinimine Ligand. To solid tBu₃P (24.8 g, 123.0 mmol) at 25° C.     was added trimethylsilylazide (2.0 mL, 15.0 mmol,). The reaction was     warmed to 90° C. After 15 minutes further azide (3.0 mL) was added     Over the next 2 hours further azide (22.5 mL) was added in 3-9 mL     aliquots (total azide added=27.5 mL, 208.0 mmol). The reaction was     stirred at 95° C. for a further 4 hours then allowed to cool     overnight before the excess azide was removed in vacuo (34.4 g, 97%) -   Metal Precursor. A solution of hexafluorobenzene (59.5 g, 320.0     mmol) in 50 mL of THF was added dropwise over 10 to 15 minutes to     two molar equivalents of sodium cyclopentadienide in THF (320.0 mL,     2.0 M, 640.0 mmol). The reaction was mildly exothermic and the     reaction was maintained at about room temperature by cooling the     reaction flask in an oil bath. On completing C₆F₆ addition, the     purple reaction mixture was heated and kept at 60° C. for 3 hours.     The reaction was allowed to cool slightly and was then added to neat     chlorotrimethylsilane (60.0 mL, 450.0 mmol) at 0° C. over 15-30     minutes. After an additional 30 minutes, the reaction was warmed to     30° C. and the THF, excess chlorotrimethylsilane and other volatiles     were removed in vacuo. The resulting wet solid was washed with     heptane and filtered to remove inorganic solids. Concentration of     the heptane filtrate in vacuo yielded an oily product, (76.6 g,     79%). Butyllithium (1.6 M in hexane, 127.0 mL, 203.0 mmol) was added     to a solution of (C₆F₅)CpTMS (58.8 g, 193.0 mmol) in heptanes (300     mL) via a dropping funnel over 40 minutes. The reaction was stirred     overnight, filtered and the resulting white solid was washed with     pentane (3×50 mL) and isolated in vacuo (59.8 g, 75%). To a solution     of LiC₆F₅CpTMS (12.0 g, 39.0 mmol) in 300 mL THF was slowly added a     solution of 1-bromohexane (64.1 g, 390 mmol) in THF (50 mL) at 0° C.     over 30 minutes. The mixture was allowed to warm to room temperature     and stirred for 3 hours. Volatiles were removed in vacuo and the     residue was triturated in pentane (2×50 mL) and volatiles were     removed. The orange oil was extracted in heptanes, filtered, washed     (3×25 mL), and concentrated to afford a golden brown oil. The oil     was added to neat titanium (IV) chloride (7.4 g, 39.0 mmol) and the     burgundy solution was stirred at 60° C. for 3 hours and the     volatiles were removed in vacuo (9.2 g, 50%). -   Final Complex. The metal precursor (9.2 g, 19.6 mmol) and the     phosphinimine ligand (5.7 g, 19.6 mmol) were weighed together into a     Schlenk flask and toluene (150 mL) added. The reaction was heated at     90° C. for 5 hours. The volume of the reaction mixture was reduced     to 15 mL and heptane (100 mL) added. The mixture was stirred     overnight and then filtered and washed with heptane. The solids     collected were dried in vacuo (11.2 g, 79%).

The aluminoxane was a 10% MAO solution in toluene supplied by Albemarle.

The support was silica SYLOPOL 2408 obtained from W. R. Grace.

Preparation of the Support (Apart from the Control)

A 10% aqueous solution of the Zr(SO₄).4H₂O was prepared and impregnated into the support by incipient wetness impregnation procedure. The solid support was dried in air at about 135° C. to produce a free flowing powder. The resulting powder was subsequently dried in air at 200° C. for about 2 hours under air and then under nitrogen at 600° C. for 6 hours.

NAA Characterization

A sample of Zr(SO₄)₂ treated SYLOPOL 2408 prepared as above was determined to have a sulfur:zirconium ratio of 0.703 by NAA analysis; which is consistent with the ratio expected for pure Zr(SO₄)₂.

XRD Analysis

A 1 gram sample of pure Zr(SO₄)₂.4H₂O was dehydrated in a muffle furnace at 600° C. for 6 hours and the solid was analyzed by XRD analysis, which showed 100% of the Zr(SO₄)₂ remained.

The above shows that zirconia is not formed by the calcination process of Zr(SO₄)₂.4H₂O at up to 600° C. under nitrogen.

To a slurry of calcined support in toluene was added a toluene solution of 10 weight % MAO (4.5 weight % Al, purchased from Albemarle) plus rinsings (3×5 mL). The resultant slurry was mixed using a shaker for 1 hour at ambient temperature. To this slurry of MAO-on-support was added a toluene solution of catalyst to give a molar ratio of Al:Ti of 90:1. After two hours of mixing at room temperature using a shaker, the slurry was filtered, yielding a colorless filtrate. The solid component was washed with toluene and pentane (2×), then ˜400 mTorr and sealed under nitrogen until use.

For the comparative example the same procedure was used except that the support was not treated with Zr(SO₄).4H₂O.

Polymerization

A 2 L reactor fitted with a stirrer (˜675 rpm) containing a NaCl seed bed (160 g) (stored for at least 3 days at 130° C.) was conditioned for 30 minutes at 105° C. An injection tube loaded in the glovebox containing the catalyst formulation was inserted into the reactor system, which was then purged 3 times with nitrogen and once with ethylene at 200 psi. Pressure and temperature were reduced in the reactor (below 2 psi and between 60 and 85° C.) and TIBAL (500:1 Al:Ti) was injected via gastight syringe followed by a 2 mL precharge of 1-hexene. After the reactor reached 85° C. the catalyst was injected via ethylene pressure and the reactor was pressurized to 200 psi total pressure with 1-hexene fed with a syringe pump at a mole ratio of 6.5% C₆/C₂ started 1 minute after catalyst injection. The temperature of reaction was controlled at 90° C. for a total runtime of 60 minutes. Reaction was halted by stopping the ethylene flow and turning on reactor cooling water. The reactor was vented slowly to minimize loss of contents and the polymer/salt mixture was removed and allowed to air dry before being weighed.

Fouling was measured by collecting the polymer from the reactor (including lumps and sheeted material) and sieving through a number 14 sieve (1.4 mm openings) the product (lightly brushing but not “pushing” product through) to determine what percent of the polymer did not pass through the sieve as a percent of the total polymer produced. The results of the experiments are set forth in Table 1 below.

TABLE 1 Time Max height AL:Ti Productivity Max to Rate of 1-10/ Molar gPE/g C₂ Max Rise Average C₂ Support ratio catalyst Flow Flow scLM/min concentration Fouling % Phosphinimnine:phenoxide 90:1 1307 1.87 3.08 0.61 2.49 14 (1:1 M/M) SYLOPOL 2408 Zr(SO₄)₂ Phosphinimnine:phenoxide 90:1 1412 2.60 3.42 0.76 5.64 56 (1:1 M/M) SYLOPOL 2408

The results show that although there was a shorter time to “light off” of the catalyst on the support treated with Zr(SO₄)₂.4H₂O and there was a significantly lower amount of fouling on the treated support than for the untreated support 

What is claimed is:
 1. A method to prepare a dual catalyst comprising (i) from 20 to 80 mole % of a phenoxide catalyst of the formula:

wherein R², R³, and R⁵ are hydrogen atoms , R¹ is a cyclohexyl radical, R⁴is methoxy radical, and R⁶ is a t-butyl radical M is selected from the group consisting of Ti, Zr and Hf, X is a chlorine atom, n is 1 or 2 and t is 2 or 3 and the sum of n+m is the valence of M. and (ii) from 80 to 20 mole % of a phosphinimine catalyst of the formula:

wherein M is a group 4 metal having an atomic weight less than 179; PI is a phosphinimine ligand of the formula:

wherein each R15 is independently selected from the group consisting of C₁₋₆ hydrocarbyl radicals; L is a monoanionic ligand selected from the group consisting of a cyclopentadienyl radical which is unsubstituted or substituted by a substituent selected from the group consisting of a C₁₋₆ alkyl radical which is substituted by 2n+1 fluorine atoms where n is the number of carbon atoms in the alkyl radical, and a C₆F₅ radical which cyclopentadienyl ligand is optionally further substituted with up to two C₃₋₆ alkyl radicals in the 2 or 3 position relative to the fluorine containing substituent; Y is an activatable ligand selected from the group consisting of a hydrogen atom, a chlorine atom and a C₁₋₄ alkyl radical ; t is 1 or 2; q is 1; and p is an integer and the sum of t+q+p equals the valence state of M.; both on an inorganic support comprising: impregnating a porous particulate inorganic oxide support having an average particle size from 10 to 150 microns, a surface area greater than 100 m²/g and a pore volume greater than 0.3 ml/g with not less than 1 wt % of a 5 to 15 wt % aqueous solution of Zr(SO₄)₂.4H₂O thereof to provide from 0.010 to 0.050 mmol of Zr per gram of treated support, not less than 1 weight % based on the weight of the support of Zr(SO₄)₂.4H₂O; (ii) recovering the impregnated support; (iii) calcining said impregnated support at a temperature from 300° C. to 600° C. for a time from 2 to 20 hours in an inert atmosphere; (iv) contacting said impregnated calcined support with a hydrocarbyl solution containing at least 5 weight % of an aluminum activator compound of the formula R¹² ₂AlO(R¹²AlO)_(r)AlR¹² ₂ wherein each R¹² is independently selected from the group consisting of C₁₋₂₀ hydrocarbyl radicals and r is from 3 to 50 to provide from 0.1 to 30 weight % of said aluminum compound based on the weight of said calcined support; optionally separating said activated support from said hydrocarbyl solution; and contacting said activated support with one or more hydrocarbyl solutions containing at least 5 weight % of a phosphinimine catalyst, a phenoxide ligand containing catalyst or both; and (v) optionally contacting said catalyst with a hydrocarbyl solution of an anti static comprising (I) from 3 to 48 parts by weight of one or more polysulfones comprising: (a) 50 mole % of sulphur dioxide; (b) 40 to 50 mole % of a C₆₋₂₀ an alpha olefin; and (c) from 0 to 10 mole % of a compound of the formula ACH═CHB where A is selected from the group consisting of a carboxyl radical and a C₁₋₁₅ carboxy alkyl radical and B is a hydrogen atom or a carboxyl radical provided if A and B are carboxyl radicals A and B may form an anhydride; (II) from 3 to 48 parts by weight of one or more polymeric polyamides of the formula: R²⁰N[(CH₂CHOHCH₂NR²¹)_(a)—(CH₂CHOHCH₂NR²¹—R²²—NH)_(b)—(CH₂CHOHCH₂NR²³)_(c)H]_(x)H_(2-x—) wherein R²¹ is an aliphatic hydrocarbyl group of 8 to 24 carbon atoms; R²² is an alkylene group of 2 to 6 carbon atoms; R²³ is the group R²²—HNR²¹; R²⁰ is R²¹ or an N-aliphatic hydrocarbyl alkylene group having the formula R²¹NHR²²; a, b and c are integers from 0 to 20 and x is 1 or 2; with the proviso that when R²⁰ is R²¹ then a is greater than 2 and b=c=0, and when R²⁰ is R²¹NHR²² then a is 0 and the sum of b+c is an integer from 2 to 20; and (III) from 3 to 48 parts by weight of C₁₀₋₂₀ alkyl or arylalkyl sulphonic acid, to provide from 50 to 250 ppm of antistatic based on the weight of the catalyst; and (vi) recovering and drying the catalyst.
 2. The process according to claim 1, wherein none of R³, R⁴, R⁵ has a Hammett s_(r) value (Hansch et al., Chem Rev. 1991, 91, 165) greater than 0.2.
 3. The process according to claim 2, wherein in the activator R¹² is a C₁₋₄ alkyl radical and r is from 10 to
 40. 